Production of monohalocycloalkanes



Prensa Feb. 24. i948 2.4mm rnoouc'rrou or mouonnpoorcwnames Louis Sohmerling, Riverside, 11L, aosignoi to Unlversal Oil Products Company, Chicago, 111., a corporation of Delaware Y No Drawing. Application March as, 194

Serial No. 528.623 1' This invention relates to the production of a halonaphthenic hydrocarbon by reaction of a naphtheni'c hydrocarbon with a halo-olefin. More specifically, the process is concerned with the condensation of a cycloparaflinic hydrocarbon and a haloolefln in the presence of a metal halide catalyst.

An object of this invention is the production of a halonaphthenic hydrocarbon, which may also be termed a halocycloalkane, by reacting a naphthenic hydrocarbon and a halo-olefin in the presence of a metal halide catalyst.

Another object of this invention is the production of amonohalocycloalicane by the condensation of a cycloparamn and a monohalo-olefin in :he presence of a catalyst of the Friedel-Crafts YD'B.

A further object of this invention is the production of a monohalo-monocycloalkane by condensing a monocyclic-cycloalkane and a monohalo-oleiln, the halogen of which has an atomic weight of from about'35 to about 80, in the presence of a Friedel-Crafts type metal halide.

A still further. object of this invention is the production of a monochloro-monocycloalkane by condensing a monocyclic-cycloalkan and Ta monochloro-olefln in the presence of a catalyst of the Friedel-Crafts type.

One specific embodiment of the present invention comprises a process for producing a monohalocycloalkane which comprises condensing a -cycloparamnic hydrocarbon and a monohaloolefin in the presence of a catalyst of the Friedel- Crafts tyne.

In this specification and in the claims, the term "naphthenic hydrocarbon is used to include the saturated monocyclic hydrocarbons having the general formula CnHzn, as well as bicyclic and polycyclic saturated compounds. The monocyclic compounds are often referred to as cycloparamns and alkyl cycloparafilns and are also known as cycloalkanes and alkyl cycloalkanes. The cycloparaflins preferably used in my process are those having and Gcarbon atoms in the ring. The lower cycloparafflns having 3 and 4 carbon atoms in the ring may also be condensed with a halo-olefin although these cycloparaflins are not to be considered on an equivalent basis with the naphthenic hydrocarbons of higher molecularweight which have rings containing 5, 6, or 7 carbon atoms per molecule.

Naphthenic hydrocarbons are available in various gasoline and naphtha fractions or they may be obtained'as reaction products from certain hydrocarbon conversion reactions, for .ex-

12 Claims. (CL 260-64?) ample, the catalytic cyclization of aliphatic hydroca'rbon's jfollowd by hydrogenation of the resultant aromatic hydrocarbons to naphthenic hydrocarbons. Naphthenic hydrocarbons which are ofp'articular interestas starting materials tor the present process include cyclohexane, methylcyclopentan, methylcyclohexane, and other alkyl or polya-lkyl cyclohexanes. In general, naphthe'nie hydrocarbons'which contain tertiary carbon atoms are preferred.

Halo-cleans which may be condensed with naphthenic' hydrocarbons according to the process of the present invention contain at least one halogen atom-and one double bond per molecule. Such halo-oleiin's comprise halo-ethenes, -propenes, -butenes, -pentenes, and halo-alkenes of higher molecular weights. Vinyl chloride, allyl chloride, nieth'allyl chloride, and the corresponding bromine 'coinpou'nds are representative of suitable lhalo-oletlns. The term halo-olefins is also used herein in reference to other unsaturated compounds of carbon, hydrogen, and halogen containing more than one halogen atom and more than one double bond per molecule; such compounds include cis-1,2-dichloro-ethylene, 1,2- dichloropnopene-Z, etc. Halo-oleflns may be formed in anysuitable manner such as by the action of ahalogen upon an oleflnic hydrocarbon at a temperature at which substitution'occurs, this temperature being generally substantially in excess of that at which addition of halogen to the oleflnic' double bond is the principal reaction. Mono-halo-olefins may also be prepared by the removal of one molecule of hydrogen halide from a dihaloallraiae. by any of several well known methods.

Catalysts of the Frledel -Crafts type utilizable in effectinglthe interaction of a halo-olefin with a cyclo-parafllndnclude metal chlorides and bromides and particularly chlorides of aluminum and iii'rconiu'r'n. Of .these' catalytic materials, aluminum chloride is generally more "widely applicable in that it'possesse's substantial cataiyue" .activity at relatively low temperatures. Metalhali'des of the Fried'el-Crafts type are employed vas,ca'talysts preferably 'at temperatures between-about -30' and about +25 0., although higher temperatures, generally not in excess of about '.C.,'Tare.also sometimes utilizable with certain reactipn in ixtures comprising essentially etc. The materials so utiliaable as carriers should- .have substantially no harmful eflect on'the catalyst activity oi. the metal halide or mixture, oi metal halides employed. In some cases, the catalyst may be dissolved in a suitable solvent such as a nitroparailin.

While the reaction oi a cycloparailin'with a halo-olefin is not understood completely, it isheassasoo lieved that it involves the addition of a cycloparamn to the double bond the halo-olefin par-- ticularly at temperatures below about 0 C. Such an addition reaction apparently results in the iormatigmoi a cycloalkyl halideoi higher boiling zpoint'than the reactants and with a molecular weight which is equal to the sum of the molecular,

weights oi the reacting cycloparamn and unsaturated halide. At a higher reaction temperature it appears that a cycloalkyl halide is first formed and then this compound undergoes an intramolecular change or hyrogen disproportionation with the charged eycloparaiiin producing a higher boiling cycloparailin and liberating hydrogen halide. In order to obtain. high yields of cyclo-v molecular proportions of cycloparaiiln per molecular proportion of halo-oleflns are present in the reaction mixture charged to the process.

The condensation or a cycloparaiiin with a halo-olefin, unsaturated halide. or 'alkenyl halide oi the type of vinyl-, allyl-. methallyl-chloride or -bromide-. etc.. is carried out using either batch or continuous operation. Thus.,i n batchtype operation a halo-olefin is added gradually to a 01' the Friedel-Crafts type. "lfhe-reaction'tem-* perature ismaintained belowabout 100C. but

preferably between about and about 25"; C. and under suilicient pressure to keep in liquid restricting the v Io! the l'riedel-Cra'its type. The mixture of cycleparaiiln.halo-olefin, catalyst. and sometimes ydrosen or a hydroien halide is directed through "a mixer or throush a reactor containing material to eflectintimate contactroithe catav lyst with the reacting hydrocarbons. The condiq tionsot temperature and pressure employed in such a condensation treatment are within the limits indicated above, but particular conditions used in any given. condensation reaction'vary with the molecular weights and reactivities oi the reactants, the concentration and activity or the catalyst employed, andother factors.

The iollowingexample is given to illustrate the character of the results obtiined' by the use oi the present process, althoughthe data presented are not introduced with the intention of unduly generally broad .scope of the invention.

250 parts by weight of methylcyclohexane, 79 parts by weight or allylchloride. and 20 parts by weight of aluminum chloride were contacted at 15 C. for two hours in a glass-lined reactor equipped with a motor driven'stirrer. The reaction product consisted or 303 parts by weight oi liquid and 46 parts by weight oi a red. viscous catalyst layer. The liquid product was then washed, dried, and distilled. Besides unconverted methyloyclohexane, this liquid product contained 12% by volume of liquid material boilingbetween 225 and 258 C. consisting oi isomeric chloropropylmethylcyclohexanes with a refractive index, 11 oi from 1.4680 to 213810 and a density oi' irom.0.93 to; 0 .98.f The reactioniproduct also 35. reactor containing a cycloparaflin and a catalyst contained about 8%.by'volume'ioi liquid products essentially propylmethyley iohexane, or an isomer 7 thereof formed by intramoleeular hydrogen-hystate a substantial proportion of'the reactants.

The reaction mixture is also agitated by stirring,

shaking, or some other suitable me'ansfto'feii'e'ct intimate contact oi the reactants and; catalyst. During this treatment. the cycloparaiiln comdrogen 1 chloride transfer between me'thylcyclohexane and chloropropylmethyluIclohex'ane.' Another run'i'n which iOO-partsby weight of.

1 methylcyclohexane. 50- by weight or allyl chloride and 10 partsbyweight of aluminum bines chemically with the halo-olefin to produce a cycloalkyl halide with a molecular weightwhich is equal to the sum oi the molecular weights of the reacting cycloparamn and hal-oleiln.

' chloride were reacted at 30 'C. 'yieldedrlil parts by weight or a condensation product boiling chielly at 70-75" C. at a pressure or 3.5 mm. of mercury and comprising essentially; chloropropyh' methyl cyclohexanes'and .isomersthereoi' with a .higher temperatures, some oi the cycloall'ryl halide may be converted intoan alkyl cycloparaillnic hydrocarbon of gasoline'bofling range. said'hydrocarbons being the principal product 01- the process when the condensation reaction'is' carried out at a temperature above about 25 C. in the presence of a catalyst of relatively high activity. At the higher reaction temperatures, .hydrogen halide is generally evolved from-the reaction Iclaimas theme-hydrocarbon with a halo-oieiinln thepresence 01 a Friedel Crai'ts metal halide catalyst at a temperaturelot irorn' about -30 C. to'

to commingle hydrogen with the reaction mixture since it has a tendency to increase the active life or the catalyst.

Continuous condensation of cycloparail'ln with a halo-olefin is carried outby introducingthe halo-olefin, also referred to as an unsaturated halide, or a mixtureof a cycloparaflln and said halide to a circulating commingled mixture oi a cycloparamn and a metal halide catalyst, particularly aluminum chloride or another compound llrefractive index, 1: 5. or from-1.4620 "to 1.4660.

Analysis of the material showed-that it contained 69.4% carbon and ldpqt hydrogen. The values calculated fora'icompound' having the formula CioHmCl are 68.8% carbon and 11.0% hydrogen. -,In this run there was also obtained 6 parts by weight of propylmethylcyclohexane or its isomers. Thenovelty a d utilityoi the procms oi-the present invention are 'evident irom the preceding specification and examples. although neither sec-;

tion isintended to unduly limit itsgenera'lly broad scope. j

inventionzl.- A process which comprises reacting a naphabout 25 C.

v 2. A-proc'ess which comprises reacting a cyclo-'v paraiilnic i'rvdrocarbon with a lmlo-joleiln in the presenceor a Friedel-Craits metal halide cataiyst at a temperatureoi from. about -30 C. to r ,about25C'. 1 3. A process. which comprises reacting a cycloparainnic hydrocarbonI-with ahalo-oleiin in the presence oi a l 'ried'el Craits metal halidecatalyst at a temperature or iron: about-30. ate-about U 25 C. under sufllcient pressure to keep in liquid state a substantial proportion of the reaction mixture.

4. A process which comprises reacting a cycloparafllnic hydrocarbon with a chloro-olefin in the presence of a Friedel-Crafts metal halide catalyst at a temperature of from about -30 C. to about 25 C.

5. A process which comprises reacting a. cycloparaflinic hydrocarbon with a bromo-olefln in the presence of a Friedel-Crafts metal halide catalyst at a temperature of from about -30 C, to about 25 C.

6. A process which comprises reacting an alkyl cyclopentane hydrocarbon with a chloro-olefin in the presence of a Friedei-Crafts metal halide catalyst at a temperature of from about 30 C. to about 25 C.

7. A process which comprises reacting an alkyl cyclohexane hydrocarbon with a chloro-olefln in the presence of a Friedel-Crafts metal halide catalyst at a temperature of from about -30 C. to about 25 C.

8. A process which comprises reacting an alkyl cyclohexane hydrocarbon and a choloro-olefln in the presence of an aluminum chloride catalyst at, g5temperature of from about -30 C. to about I 6 9. A process which comprises reacting an alkyl cyclohexane hydrocarbon and a monochloroolefin in the presence of an aluminum chloride catalyst at a temperature of from about 30 C.

to about C.-

10. A process which comprises reacting methyl cyclohexane and a chloro-olefin in the presence of an aluminum chloride catalyst at a temperature of from about C. to about 25 C.

11. A process which comprises reacting methyl cyclohexane and a monochloro-olefin in the presence of an aluminum chloride catalyst at a temperature of from about 30 to about 25 C.

12. A process which comprises reacting methyl cyclohexane and allyl chloride in the presence of an aluminum chloride catalyst at a temperature of from about 30 C. to about +25 C.

LOUIS SCHMERLING.

REFERENCES CITED The following references are of record in the file of this patent:

"Chemical Abstracts," vol. 35, cols. 3980-1 (1941). 

